Amine salts of polychloro-2-hydroxy-diphenyl



atented Mar. 25,1947

AMINE SALTS F POLYCHLORO-Z- HYDROXY-DHHENYL Gerald H. Coleman and Wesleyl). Schroeder,

Midland, Mich, assignors to The Dow Chemical Company, Midland, Mich, acorporation of Michigan No Drawing. Application October 24, 1941, SerialNo. 416,370

2 Claims.

The present invention relates to amine salts ofpolychloro-2-hydroxy-diphenyls; and is particularly concerned withcompounds having the following formula:

wherein X represents a member of the group consisting of hydrogen andchlorine, each R is selected from the group consisting of alkyl,cycloalkyl, aralkyl, and hydroxy-alkyl radicals, and n is an integer notgreater than 3. These compounds are useful as parasiticides and asstabilizers in ethers and plastic compositions.

We have prepared representative members of the above-identified group ofcompound and found them to be crystalline white solids or viscousliquids somewhat soluble in many organic solvents, and relativelyinsoluble in water. These compounds are relatively stable to light andair, are not appreciably affected by carbon dioxide, and arenoncorrosive to the skin of humans and higher animals. l

The new compounds are prepared by reacting a suitable amine compoundsuch as N. N-dibutyl amine, triamyl amine, octyl amine, cyclohexylamine, N-cyclohexyl-dimethyl amine, N-propyldiethanol amine,c-phenylethyl amine, N-benzylcyclohexyl amine, benzyl amine, diethanolamine, triethanol amine, etc. with a polychloro-Z-hydroxy-diphenyl.Substantially equimolecular proportions of thepolychloro-2-hydroxy-diphenyl and amine have been found to give thedesired salts in good yield, although any suitable amounts may beemployed. Where an excess of one or .the other reactant is present,purification may be accomplished by extracting the crude salt productwith a selective solvent for the 2-hydroxy-diphenyl compound, amine, oramine salt. In most instances, however, the crude reaction productconsisting essentially of the amine salt is adapted to be employed as aparasiticidal toxicant or stabilizer without further treatment.

In preparing the foregoing compounds, a solvent such as benzene,chlorobenzene, toluene, petroleum ether or alcohol may be employed inthe reaction mixture. The operating temperatures are not critical andmay vary from room temperature to about 120 C. When a solvent isemployed, the reaction is conveniently carried out at the refluxingtemperature of the reaction mixture. The reactants may simply be mixedtogether to accomplish the reaction which is accompanied by thedevelopment of considerable heat. Where the crude product iscrystalline, purification may be accomplished by crystallization fromvarious organic solvents and mixtures of solvents. When a liquid productis obtained, it may be clarified by treatment with bone charcoal orabsorbent earths, if desired.

A preferred group of amine salts falling within the scope of the presentinvention are those of 3.5.x-trichloro-2-hydroxy-diphenyl. Thesecompounds have been found particularly valuable as toxicants in ovicidalmixtures.

The following examples set forth specific embodiments of the inventionbut are not to be construed as limiting the same.

Example 1 23.9 grams (0.1 mol) of 2-hydroxy-3.5dichlorodiphenyl and 12.1grams (0.1) of N-benzyl methylamine were mixed together. Considerableheat of reaction was developed. The mixture was stirred and heated on asteam bath, and thereafter cooled to obtain the N-benzyl methylamineaddition salt of 2-hydroxy-3.5-dichloro-diphenyl as a thick viscous oilhaving a specific gravity of 1.214 at 25/25 C. This compound is solublein 95 per cent ethanol and in carbon tetrachloride, slightly soluble inkerosene, and soluble in water to the extent of 0.009 per cent at 24 C.The saturated water solution has a pH of 9.5.

Example 2 27.34 grams (0.1 mol) of 3.5.x-trichloro-2-hydroxy-diphenylwas dissolved in milliliter of hot petroleum ether. 9.9 grams (0.1 mol)of cyclohexyl amine was added to the petroleum ether solution withstirring and the mixture cooled to room temperature. The amine saltprecipitated from solution and was recovered by filtration, wherebythere was obtained 28 grams of a product melting at 137.5-l38.5 C. Themonocyclohexyl amine salt of 3.5.x-trichloro-2-hydroxy-div phenyl wasfound to be slightly soluble in water, soluble in per cent ethylalcohol, and insoluble in carbon tetrachloride and kerosene.

Example 3 In a similar manner 0.1 molar amounts of3.5.xtrichloro-2-hydroxy-diphenyl and N.N-dieyclohexyl amine werereacted together in petroleum'ether to obtain 40.5 grams of theN.N-dicyclohexyl amine salt of 3.5.x-trichloro-2-hydroxy-diphenyl as awhite crystalline compound 3 melting at 155.5-15'7 C. This product isinsoluble in water, carbon tetrachloride and kerosene, and soluble in 95per cent ethyl alcohol.

18.2 parts by weight of this compound was ground with 72.7 partsv ofdiatomaceous earth and 9.1 parts of sodium lauryl sulphate. The

resulting concentrate was diluted with sufficient water to give aconcentration of 0.5 pound of amine salt per 100 gallons. This spraygave a kill against Colorado potato beetle larvae of 82 per cent.

Example 4 12.85 grams of the long chain aliphatic amines obtained by thecarboxylic reduction and ammonification of the mixed acids derived fromthe hydrolysis for coconut oil, and 27.3 grams of3.5.X-trichloro-Z-hydroxy-diphenyl were mixed together and heated at6040 C. for approximately 1 hour. The mixture was then cooled to roomtemperature to obtain a quantitative yield of the coconut oil amineaddition salt of 3.5. trichloro-2-hydroxy-diphenyl product as asemisolid grease insoluble in water, slightly soluble in kerosene, andsoluble in carbon tetrachloride and 95 per cent ethyl alcohol.

Example 5 2?.34 grams (0.1 mol) of 3.5.X-trichloro-2-hydroXy-diphenyland 16.1 grams (0.1 mol) of N- normahbutyldiethanol amine were mixedtogether and heated at 70-80 C. for approximately 1 hour. Upon coolingthere was obtained a dark red viscous oil having a density at 25 C. of1.198 grams per cubic centimeter. This N-normal butyidiethanol amineaddition salt of 3.5.x-triohloro-2 hydroXy-diphenyl product wasinsoluble in water, slightly soluble in kerosene, and soluble in 95 percent ethyl alcohol and carbon tetrachloride.

This product was dispersed in a 2 per cent oil emulsion in amountsufficient to provide 1 pound of the amine salt per 100 gallons ofemulsion to obtain a spray composition which gave a control of 80.6 percent against the eggs of L. Kalmzz' stal.

Example 6 In a, similar manner equimoleoular proportions of N.ll-di-normal-butylmonoethanol amine and3.5.x-trichloro-2-hydroXy-cliphenyl were reacted together to obtain aquantitative yield of the addition salt or the amine and phenol as aviscous dark oil having a density of 1.205 grams per cubic centimeter at25 C. This product was insoluble in water, sli htly soluble in kerosene,and soluble in 95 per cent ethyl alcohol and carbon tetrachloride.

The 3.5.X-trichloro-2-hydroxy-diphenyl employed as a starting materialin the preparation of certain of the amine salts set forth in theforegoing examples was prepared by reacting 2- hydroxy-diphenyl withgaseous chlorine. In a representative preparation 0.5 mol of2-hydroxydiphenyl was dissolved in milliliters of tetrachloro-ethyleneand the solution heated to C. Chlorine gas was passed through the phenolsolution at this temperature until the amount of hydrogen chlorideevolved indicated the reaction of 3 mole of chlorine. The crude reactionproduct solidified upon cooling, and was dissolved in hot petroleumether and recrystallized. After several recrystallizations, there wasobtained a 49 per cent yield of 3.5.X-trich1oro-2- hydroXy-diphenyl as awhite solid melting at 117-l18.5 C. This compound was substantiallyinsoluble in water, slightly soluble in kerosene, and somewhat solublein carbon tetrachloride and 95 per cent ethyl alcohol. Upon analysis,the phenol was found to contain 38.95 per cent chlorine as compared to atheoretical chlorine content of 39 per cent. The position of the thirdchlorine atom in the hydroxylated benzene ring was determined by theoxidation of the compound to form benzoic acid.

We claim: 1. A compound having the formula:

NBA- (cycloalkyl) wherein n represents an integer not greater than 3,such compound being prepared from a 3.5.xtrichloro-2-hydroxy-diphenylmelting at 117- 118.5 C.

2. N.N-dicyclohexylamine salt of 3.5.x-trichloro-2-hydroxy-diphenyl,such compound being prepared from a 3.5.x-trichloro-2-hydroxydiphenylmelting at 117-l18.5 C.

GERALD H. COLEMAN. WESLEY D. SCHROEDER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,222,486 Moore Nov. 19, 19402,189,420 Hockenyos Feb. 6, 1940 1,992,577 Moness Feb. 26, 19351,940,817 Semon Dec. 26, 1933 1,919,298 Lehman July 25, 1933 1,852,787Murrill Apr. 5, 1932 1,852,820 Murrill Apr. 5, 1932 FOREIGN PATENTSNumber Country Date 609,164 German Feb. 8, 1935

